Guanamines in textile finishing



-Patented Sept. 25, 1945' GUANAMINEB IN TEXTILE FINISHING Jack '1.Thurston, Cos Cob, Coma, assignor to American Cyanamld Company, NewYork, N. Y., a corporation of Maine No Drawing. Application August 30,1941, Serial No. 409,113

3 Claims. (01. 117-161) This invention relates to the treating andfluishing of textiles and textile forming materials such as cotton,linen, wool, viscose, cellulose acetate, spun rayon, and the like. Moreparticularly the invention relates to textile finishing processes, tofinishing compositions and to textiles finished with compositionsconsisting of or containing N-substituted guanamines and their aldehydecondensation products as will be subsequently described.

A wide range of softening agents, fulling agents, lubricants,creaseproofing agents and waterproofing agents have heretofore beenapplied to textile threads and fibers. The treatment of textiles forthese and similar purposes such as shrinkproofing is known as textilefinishing, and the agents employed for the purpose are known as textilefinishing agents. It is a principal object of the present invention toprovide a new class of textile finishing agents having improvedsoftening, waterprooflng and other properties, and to provide new andimproved textile finishing processes employing such materials. A furtherimportant feature of the invention resides in the provision of cotton,wool, silk, cellulose ester and other yarns, threads or fabrics finishedwith compositions containing N-substituted guanamines and their reactionproducts and having improved water-re-' sistance and a more desirablehand, and other properties.

In my eopending application Serial No. 409,112, filed concurrentlyherewith, I have shown that the 2-alkyl or cycloaliphatic4,6-dia1nino-1,3,5- triazines, generally known as alkyl guanamines, areexcellent softening agents and water-repellents for textiles when thealkyl group contains at least seven carbon atoms. The present inventionis based on the discovery that the textile softening and water-repellentproperties of the guanamines are not necessarily limited by the presenceof a long alkyl chain or cycloaliphatic group on the 2 carbon atom, butthat one or more substituent group or groups totalling seven carbonatoms may be located at any point or points about the guanamine nucleuswith equally eifective results. Since the only groups capable ofsubstitution other than the 2 carbon atom are amino groups it followsthat the compounds in question are all N-substituted guanamines whichmay or may not contain substituents on the 2 carbon atom.

Many of the N-substituted guanamines of my present invention possess anumber of distinct advantages over some of the higher alkyl guanaminesfor textile finishing, such as greater ease of preparation, improvedcompatibility with certain resins and other binding agents, and bettersoftness of hand. Thus, for example, it is a known fact that the loweralkyl guanamines are more easily prepared, and with much better yields,than are the higher alkyl guanamines, and this also applies toN-substituted lower alkyl guanamines prepared from substitutedbiguanides and lower fatty acid esters. Moreover, the N-substitutedguanamines are obtainable by fusing the corresponding unsubstitutedguanamines with amine salts or with acid chlorides or anhydrides. Mypresent invention therefore extends the field of guanamines availablefor textile finishing to include a large number that may be cheaply andeasily prepared.

Although any N-substituted guanamine in which the substituent groupscontain a total of seven carbon atoms may be used with success inpracticing my invention I prefer those compounds in which at least oneN-substituent contains at least four carbon atoms. This substituent maybe an alkyl group, as in the N-butyl, N-amyl or N-decyl guanamines or anacyl group as in the N-butyryl and N-caproyl guanamines or it may be anaryl group as in the 4-N-phenyl guanamines, but in the latter case it ispreferable to have an aliphatic or cycloaliphatic radical of at least 4carbon atoms elsewhere in the guanamine. Although my invention is notlimited to any theory of operation, I believe that these substituentgroups extend the area covered by the guanamine when applied to textilefibers and assist in rendering the textile soft and water-repellent.

From what has been said it is evident that the N-substituted guanaminesused in practicing my invention are compounds corresponding to theformula ing monovalent radical connected to the 2-carbon atom of theaminotriazine nucleus by a carfore; and X is a saturated or unsaturatedaliphatic or cycloaliphatic group or any suitable bon-to-carbon bond, Aand B may be hydrogen 'or-any suitable monovalent substitutentthereguanamines are'i'nost useful as textile finishing agents whencombined with aldehydes. When dispersible resins are desired it isusually advisable to employ guanamines containing at least tworeplaceable amino hydrogen atoms and to use rather mild conditions forthe aldehyde condensation, such as by agitating the aldehyde and guaoxy,oxyaryl, aryiolw. orcarboxyiic, sulionic, carbonyl, amino or amido orother groups as will subsequently be explained. A few. representativecompounds illustrative of the large number which may be ,applied totextiles in accordance with the present invention are as follows:

(1) Representative N-substituted guanamines in which R is hydrogen or analkyl group are 4- N-phenyi lauroguanamine, 4-N-phenyl (2'- naminesolution at 50-70" C. until the reaction is complete,rand an inertsolvent may be used to maintain-the guanamine in a dispersed form atthese temperatures. The resulting resin solutions which are first formedcan usually be diluted with 7 limited quantities of water, but uponcontinued heating or upon reaction at higher temperatures a hydrophobicresin is produced. Further polymerization is obtained upon heating theresin after its application to the textile fibers, and a V permanentlaundry-resistant waterproofing effect ethyl) hexanoguanamine,4-N-phenyl octanoguanamine, 4-N-phenyl hexanoguanamine, 4-N- phenylbutyroguanamine, 4-N-pheny1 acetoguanamine, 4-N-phenyl (Z-methoxy)propionoguanamine, 4-N-hydroxyphenyl butyroguanamine, 4-N-m-aminophenylbutyroguanamine, 4- N-cyclohexyll-ethyl) -hexanoguanamine, 4-N- lauroyllauroguanamine, and 4-N-octanoyl octanoguanamine. Typicaltormoguanamines that may be employed include -n-p-tertiary amylphenyliormoauanamine and 4-N-butyl-4-N- phenyl formoguanamine.

(2) Typical compounds in which R is aromatic are 4-N-phenylbenzoguanamine, 4-N-cyclohexyl benzoguanamine and 4-N-butylbenzoguanamine. Other compounds typical of the large number that may beemployed in practicing the invention include N,N'-disubstitutedguanamines such as 4,6-N,N-dibutyl benzoguanamine, 4,6- N,N'-dimethylhexanoguanamine, 4,6-N,N'-diamyl benzoguanamine, 4,6-N,N'-diethanollauroguanamine, and 4-N-phenyl-6-N-myristoyl myristoguanamine.

The above and other guanamines falling within the scope of the inventionmay be prepared by reacting biguanide or substituted biguanides withunsubstituted or substituted aliphatic and cycloaliphatic carboxylicacids and their esters and halides. When the acid halides are used thereaction usually proceeds smoothly upon simple admixture of the reagentsin the presence of inert solvents but when the esters are employed it isfrequently desirable to carry out the reaction in the presence ofalkaline catalysts. Metal alcoholates are particularly useful for thispurpose, and sodium methylate is the preferred catalyst. Thecondensation product is usually recovered by filtration and purified byrecrystallization from methanol, other alcohols, acetone, methyethylketone, hot water or other suitavle solvents. Many of the N-substitutedguanamines may also be prepared from the corresponding unsubstitutedguanamines by fusion with amine salts, preferably in the presence of aflux such as phenol and a condensation catalyst such as zinc chloride.N- acylguanamines may be prepared in similar manner by heating theunsubstituted guanamine with an acid anhydride or with an acid chloride,preferably in the presence of a strong trialkyl amine.

All of the N-substituted guanamines containing at least one free aminohydrogen will comblue with formaldehyde, acetaldehyde, butyraldehyde andother aldehydes to form condensation products. This is an importantadvantage of my invention, for many of the N-substituted is obtainedwhen the fiber is first impregnated with the resin in itswater-dispersible stage and then subsequently heated to further cure theresin to the water-insoluble stage.

Although other aldehydes may be employed I prefer to condense theguanamines with formaldehyde, which may be used in the form of ordinary37% formalin solutions, or as strong aqueous formaldehyde solutions of40-50% strength stabilized by the addition of 4-10% of melamine, or aparaformaldehyde. At least one mole of formaldehyde for each mole ofguanamine shouldbe used, but two to ten moles of formaldehyde arepreferred. When higher formaldehyde ratios of the order of 6-8 moles foreach mole of the guanamine are employed the condensation product is moreeasily dispersible in water.

The guanamine-formaldehyde condensation .products, are quite easy toobtain in the form of substantially monomolecular products; that is tosay, as methylol guanamines. These compounds can be alkylated by heatingwith primary alcohols such as methanol, ethanol and butanol with orwithout the addition of small amounts of phosphoric acid, oxalic acid orhydrochloride acid with azeotropic distillation of the water ofcondensation, and the resulting products may be applied to textiles fromtheir solutions in organic solvents as creaseproofing agents andwater-repellents.

Many of the N-substituted guanamines are soiuble in such organicsolvents as acetone, toluene, dioxane and ethers of ethylene glycol andmay 'be applied as such to textiles as softening agents andWater-repellents. The aldehyde condensation products can also be appliedas solutions in these and similar organic solvents. In addition to thedispersi'bility obtained by the use of mild temperature conditionsduring the condensation and by excess formaldehyde, referred to above,the condensation products can be dispersed in water containingequimolecular amounts of organic acidssuch as acetic, lactic andalpha-hydroxy isobutyric acids, and these acids will also act as curingaccelerators for the resins after their aplication to the cloth. Theresins are also solubilized by ammonia and other alkalis. Polymerizationproducts obtained by heating glycidol and other alcohols containing anethylene oxide ring are also good dispersing agents.

Another class of agents that are well suited for use as dispersingagents are aliphatic and cycloaliphatic substituted guanamines in whichthe allryl radical contains the sulfonic group, such as omega-sulfodecanoguanamine or one or more carboxylic acid groups such asomega-carboxy propionoguanamine, omega-carboxy pelargonoassures I whichtheB-aliphatic or cycloaliphatic substitalkyl guanamine resins is'theguanamine obtained by condensingbiguanidewith"Petrex which is a dienecondensation product. of. pinene with maleic anhydride.

Additional solubilizing and dispersing agents are also described andclaimed in the copending applications or Stiegler, 'l 'luck andThurston, Se-

rial-No. 109;114 filed concurrently herewith. -As' is pointed outin-that application, such wetting and emulsifying agents assodiumisopropyl naphthalene sulionate, sodiumlauryl sulfate, glycerine andother polyhydric alcohols, partially or completely neutralized sulfitecellulose liquor, so-

dium; ammonium and ethan'olamine stearate,

oleate' and other higher'fatty acid salts and ammonium caseinate may beused as dispersing agents for the preparation of textile ilnishin'gbaths containing higher guanaminesand guanamine-aldehyde condensationproducts.

Iii-addition to the application of the N-substituted guanamines'andtheir aldehyde condensation products to textiles as the principalfinishin8 agent thesecompounds maybe applied in admixture with resins,gums, balsams and other binders that will give increased permanency tothe finish. ThuaYoi-"example, urea-formaldehyde resins,melamine-formaldehyde resins, phenolformaldehyde re'sinaalky'd resinsand any other curing typ of resin may be used to assist in binding theguanamine' tosthe fiber. These additional binding agents canbe used inconsiderable excess over -the amount or guanamine or guanamine resin,and the retention of finish on the fiber aiter laundering is therebygreatly improved. I

, 'Ashas been stated above, one of the most useful methods of preparingtextile treating baths containing' the N-substituted guanamine compoundsis with the'aid oi dispersing agents. A typical procedure of this kind,which may be used for applying any oi'the compositions of my inventionto; textiles, is as follows: g

'A solution of the N-substituted guan'amine or guanamine-aldehyderesini'sprepared in methanol, ethanol, isopropanol, ethyl ether oi ethyleneglycol or other suitable solventby heating with agitation. aqueousdispersion of a resin, gum

or other suitable binding agent is then prepared having a 'cencentrationsuitable for application to the iiberj' ior example, a solution "of10-15 parts or more of water-soluble urea-formaldehyde resin or ofmethylated trimethylol or hexamethylol melamine in suilicient watertomake 100 parts.- About 5-40 parts by weight oi" a 5% solution of asuitable dispersingagent such as sodium i'sopropyl naphthalene sullonateis'added to this bath and the guanamine or guanamine'resin solution ispoured in with stirring-while maintaining the temperature at about 115F. A dispersion having an extremely nne particle size is thus obtained,to which a curing accelerator may be added to speed up the setting ofthe resin after its ap lication to the fiber if desired. Four. percentbased on the: total resinsolids of a mixture of 4 parts hexamethylenetetramine and parts 0! diammonium phosphate has been used to advantage.The cloth to be treated'lsilnmersed in thi bath and then passed throughsqueezing rolls adjusted to a tension such that the quantity oi treatingsolution retained on the cloth is approximately equal to the weight ofthe ilber. The treated cloth is then-dried at about 250 1". and heatedfor a short time at higher temperatures to cure the: resin. A permanentand laundry-resistalntt 1:vaterproof finish is thereby imparted to the co I It'should be understood that the above described aqueous dispersionsof higher alkyl guan'amines in admixturewith urea-formaldehyde andparticularly methylated, melamine-formaldehyde resins is not claimed assuch in the present application. On the'contrary', these dispersions andtheir application to textiles are claimed in the application ofStiegler, 'Fluck and Thurston, referred to above.

The invention will be illustrated 1.. greater detail by the followingspecific examples, which show representative compositions includedtherein. It sbouldbe understood, however, that although these examplesmay describe in detail some of the more specific details of theinvention they are. given primaril for illustrativepurposes and theinvention in its-broader aspects is not limited thereto.

Example 1* 4-N-phenyl stearoguanamine was prepared by reacting 35.4parts by weight of phenyl biguanide with parts of methyl stearate in amixture of 200 parts. methanol'and 50 parts, 01 cellosolve." The productwas purii'ied by recrystallization from carbon tetrachloride.

I 40 parts by weight or 37% aqueous formaldehyde solution were adjustedto a pH of 8.0 by the addition of triethanolamine and 45 parts or the Ii-N-phenyfstearoguan'amihe and an equal weight of methanol were added.The mixture was heated at 70 C, jfor one hour, cooled and-dehydrated.The resinous product was tested as a water-repellant for cotton and spunrayon cloth.

Emmple 2 43 parts by weight or benzoguanam lne, 22 parts or n-butylaminehydrochloride and 15 parts of phenol were heated .togetherfor 6 hours at180- 225 C. The hot mixture was mixed with water, an excess ofstrong-alkali was Iaddedand the phenol was removed,"leaving' a granularsolid The resulting 4+N-butyl benzoguanamine was recrystallized from amixture of benzene and sol vent naphtha and a' pure product was obtainedin the form-of minute, colorless crystals."

This product was tested as a. water-repellent for textiles. Aformaldehydecondensation prodnot was also'prepared by-reacting 10 partsby weight of the product with 133 parts by weight of 37% aqueousformaldehyde solution, this constituting a molar ratio of 1:4. Themixture was heated to boiling during 30 minutes with agitation .and asmall amount 01' a 1%:solutionof dihydrogen dimethyl pyrophosphate wasthen added as a catalyst. The mixture was refluxed'i'or 30 minutes, anexcess of butanol was added, and the mixture was heated for anadditional .30 minutes with distillation of a water-butane] mixtureuntil a clear-resin solution was obtained. This resin solution wasapplied to spun rayon challis-i'rom a 1.5% solution in ethyl-alcoholwhich also contained 10% of urea-formaldehyde resin and 5%oi' a curingaccelerator. After drying and curing the fabric was found to possess afull, soft hand and good water repellency.

Example 3 4,6-N,N'-dibutyl benzoguanamine was prepared by fusing 140parts by weight of n-butylamine hydrochloride with 100 parts ofbenzoguanamine in the presence of 50 parts of phenol and 13.6 parts ofzinc chloride. Upon recrystallization from methanol the product wasobtained in the form of minute, colorless plates. It was tested as awater-repellent and softener for textiles.

4-N-dimethyl hexanoguanamine was prepared by fusing 103 parts ofhexanoguanamine with 40.8 parts of dimethylamine hydrochloride followedby solution in benzene and precipitation with naphtha. 10.5 parts of theproduct were reacted with 162 parts of 37% formalin by heating themixture to boiling, adding a small quantity of dihydrogen dimethylpyrophospha-te catalyst, and refluxing for one-half hour. An excess ofbutanol was then added and the mixture boiled for one-half hour longer,whereupon a clear, water-white resin solution was obtained. This productwas also tested as a textile finishing agent.

4,6'-N,N'-diacetyl decanoguanamine was prepared by refluxing 24 parts ofdecanoguanamine with 250 parts of acetic anhydride for 30 minutesfollowed by evaporation to dryness and re crystallization from ethylacetate.

Example 4 To 31 parts of neutral l-butylbiguanide sulfate 3 guanaminewas approximately 50%, the other 50% being the guanamine.

parts by weight of 37% formalin were neutralized to a pH of 8 by theaddition of triethanolamine and 16.8 parts of 4-N-octanoyloctanoguanamine and 100 parts of isopropanol were added. The mixture washeated with agitation, 100 parts of butanol were added, and the heatingwas continued under a reflux condenser for minutes. The isopropanol wasthen distilled off and the product was cooled and filtered. Theresulting clear resin solution was tested as a textile finishing agent.

Example 6 A suspension of 21.8 parts by weight of biguanide sulfate in200 parts of water was cooled to 5-10" C. and reacted with 16 parts ofsodium hydroxide. 21.8 parts of lauroyl chloride were then added withstirring and the mixture was maintained at 05 C. for two hours. 1000parts of water containing 10 parts of acetic acid were then added andafter stirring for a short time the product was filtered. The wet solidremaining on the filter was dissolved in hot ethyl acetate and theresulting solution was filtered and cooled to low temperatures. Crystalsof 4-N-lauroyl lauroguanamine were obtained which were further purifiedby recrystallization from chloroform and ethyl acetate. The purifiedproduct, which melted at 182-1835" C., was used as'a textile finishingagent.

Example 7 The hydrophobic properties of cloth treated withwater-repellant compositions containing N- substituted guanamines of thetype described in the foregoing examples were determined quantitaotively by a standard spray test, which is applied as was concentrated toabout one-third of its orig inal volume and diluted with about 400 partsof water. After removing the water-insoluble 4-H-butyl-2-ethylhexanoguanamine, it was dried and yield of a productmelting at 131-132 C. was about 30% 10 parts of the4-N-butyl-2-ethylhexanoguanamine were added to 30 parts of 37% aqueousformaldehyde containing sufilcient NaOH to adjust the pH to about 8.5.The mixture was heat ed to a clear solution after which an excess ofn-butanol was added and a butanol-water mixture distilled off until awater-free resin solution was obtained.

1 Example 5 To 145 parts of biguanide suspended in 1200 parts of acetonecooled to about 30 C. was added rapidly 117 parts of caprylic acidchloride. The reaction mixture was stirred in the cold for several hoursand finally heated to reflux and filtered. From the cold acetonefiltrate there was obtained 56 parts of octanoguanamine melting at166-167 C. The acetone insoluble residue was extracted with about 1500parts of cold water in order to remove the biguanide hydrochloride.Alter filtering and drying, there was obtained 85 parts of crude4-N-octanoyloctano guanamine melting at 184 C. This product wasrecrystallized from a 2:1 mixture oftoluene and methanol and thepurified material melted at 197-198 C. The yield of the acylatedrecrystallized from naphtha (90-125 0.) The I follows:

A six-inch square of cloth treated with the waterproofing agent, driedand cured is weighed and then suspended 10 inches from a horizontalspray nozzle supplied with water at 70 F. under a head of exactly 6feet. The cloth is sprayed for one minute, during which time 1.5 gallonsof water are discharged through the nozzle, drained for 10 seconds,rolled between pieces of absorbent paper to remove surface water, andagain weighed. The increase in weight is expressed as percent waterabsorbed, based on the original dry weight of the cloth.

In order to measure the resistance of the finish to laundering, samplesof the treated cloth were washed in an 0.5% soap solution at 160 F. for

80 minutes, rinsed and dried, and again subjected a mixture of 4 partshexamethylene tetramine and 30 parts diammonium phosphate. x 80-4 yardcotton percale was padded in the bath, passed through squeeze rolls,dried at 250 F. and cured in the manner previously described. The

results obtained are summarized in the following table:

Percent water Mom! absorbed Compound r ti oi OHIO 4 An Original Bowingi-N-ghenyl stearoguanamine 1:2. 6 36. 1 25. 4-N- utyi benzoguanamineNone 55.6 40 4,6-N,N-dibutyi benzoguanamine None 54. 3 38.4-N-butyi-2-(2-ethyi) hexanoguanamine 1:1 46.8 42. 4-N-octanoylootanoguanamine. 1:5 31. 0 26. i-N-lauroyi lauroguanamine None 39. 3 28.4,6-N,N'-diacetyl decanoguanamine None 59.

What I claim is f l. A method of finishing textiles which comprises thesteps 01' applying thereto a formaldehyde condensation product of anN-substituted guanamine of the formula B N/ x in which R is a member ofthe group consisting of hydrogen and carbon-containing monovalentradicals connected to the 2-carb0n atom of the aminotriazine nucleus bya carbon-to-carbon bond, IA and B are members of the group consisting ofhydrogen and monovalent substituents for hydrogen and X is a member ofthe group consisting of aliphatic, cycloaliphatic and mononucleararomatic radicals and in which a total of at least '7 carbon atoms iscontained in the groups R, x, A and B, and then heating the textiles tocure the guanamine-formaldehyde condensation product thereon.

2. A method of finishing textiles which comprises the step of app yingthereto an N-substituted guanamine as defined in claim 1 together with aheat-curing resin other than an N-substituted guanamine-formaldehyderesin.

3. A method of finishing textiles which comprises the steps or preparinga liquid finishing composition containing an aqueous dispersion of aformaldehyde condensation product of an N- substituted guanamine of theformula in which R is a member of the group consisting of hydrogen andcarbon-containing monovaient radicals connected to the 2-carbon atom ofthe aminotriazine nucleus by a carbon-to-carbon bond, A and B aremembers of the group consisting of hydrogen and monovalent substitutentsfor hydrogenand x is a member of the group consisting of aliphatic,cycloaliphatic and mononuclear aromatic radicals and in which a total ofat least 7 carbon atoms is contained in the groups R, X, A and B,impregnating the textiles with said composition, and heating theimpregnated textiles to dry the same and set the finish on the'fibersthereof. i I

JACK T. T'HURS'I'ON.

